Explosive compounds



Patented Jan. 28, 1947 NITED STATES PATENT EXPLOSIVE COMPOUNDS John D.Brandner, West 'Walker Township,

Schuylkill County, Pa., assignor to Atlas 'Powder Company, Wilmington,DeL, a. corporation of Delaware No Drawing. Application October 21,1944,

Serial No. 559,831

The present application relates to explosives.

An object of the present invention is the provi sion ofdiisopropanolamine trinitrate.

Another object of the present invention is the provision of a method forthe preparation of diisopropanolamine trinitrate.

A further object of the present invention is the provision of animproved detonator.

It has been found that the new compound, diisopropanolamine trinitrate,has unusual properties as an explosive and that it is particularlyapplicable as an explosive compound in detonators.

A preferred method for the preparation of diisopropanolamine trinitrateaccording to the present invention includes first reactingdiisopropanolamine with dilute nitric acid with the resultant productionof the nitrate salt of diisopropanolamine, concentrating the nitratesalt solution, reacting the concentrated solution with a concentratednitric acid solution, drowning the reacted nitration mixture in coldwater, and

separating the precipitated crude diisopropanol- This crude product maybe itin hot water, cooling the solution, and separating the purifiedprecipitated diisopropanolamine trinitrate.

The equations for these reactions may be represented as follows:

H H H O H H O H HC-G-O HC-C-C H H H H H H NH+HNOa NHg N03- H H H H H HHCC-C HC-C-C H O H H O H H H Dilute Diisopropanolnitric Nitrate salt ofamine acid diisopropanolamine H v H H HCCC H H H\ /NH2 N0 -+2HNO H H HConcentrated HCCC nitric acid H O H H 02 N H O H HC-CC H H H /NHN03+2H2O H H H HO-C-O H O H N 02 Diisopropanolamine 'trate Itis readilyseen from the above description 3 Claims. (Cl. 260-467) 2 of its processof preparationthat 'diisopropanolamine trinitrate possesses the valuableproperty of solubility in 'hot water and relative insolubility in coldwater. This property readily distinguishesit from such other alkylolamine nitrates asdiethanolamine trinitrate and monoethanolamine'dinitrate which. are water soluble compounds, as is alsomonopropanolamine dinitrate. Consequently, all of these compoundsrequire complex solvent drowning procedures to separate them fromnitrationmixtures.

Diisopropanolamine trinitrate is obtained as a white crystalline solidhaving a melting point of 119.6" C. It dissolves readily in hot waterwithout decomposition. It is a powerful secondary explosive material,highly resistant to shock and friction, but it is readily initiated bythe common primary detonator compositions. Stability tests show it tohave satisfactory heat stability. In the standard Abel heat test at160'F., diiso propanolamine trinitrate produced no effect on thestarch-jpotassiumiodide test paper during a test period of 60 minutes.

- Diisopr'opanolam-ine trinitrate may be employed to .particularadvantage as an explosive ingredient in detonators, and it findsespecial utility as asecondary detonating, or base charge,

material.

A number of specific embodiments of the invention are contained in thefollowing examples:

Example ,I

This example shows a preparation of diisopropanolamine trinitrate.

100 grams of diisopropanolamine, a soft, white, waxy solid, weredissolved in 2'7 grams of water with slight warming. 67.1 grams ofnitric acid wereplaced in a beakersurrounded by icesalt bath andequipped witha thermometer and a mechanical stirrer. The amount of waterin the diisopropanolamine solution and in the nitric acid solution wassumcient to give a concentration of 50% nitric acid on mixing, Thediisopropanola-mine solution was slowly run into the nitric acidsolution from a dropping funnel. The reaction progressed smoothly. Themaximum temperature reached was 12 C., and the total time of additionwas 1 hour and 35 minutes. The reacted'mixture was evaporated on a steambath for two hours. The theoretical yield of nitrate salt ofdiisopropanolamine was 143.7 grams and the actual yield of product was151 grams, indicating the presence of residual water. The product was'inthe form of a thick yellow syrup.

604 grams of 96.8% nitric acid in a 1 liter beaker were cooled in anice-salt bath. With rapid agitation, the nitrate salt ofdiisopropanolamine was run into the-acid through a dropping funnel. Theviscosity of the nitrat'e salt made the feed rather slow. The time ofnitration was 1 hour and 23 minutes. The maximum temperature reached was7 C., but the average temperature was about 5.5 C. The nitration mixturewas drownedin 1335 cc. of water contained in a beaker surrounded by anice-salt mixture. The time of drowning was 53 minutes andthe maximumtemperature was 9 C. .Diisopropanolamine trinitrate came down as a finewhite precipitate which was filtered and washed with 500 cc. of water ata temperature of 8 to 9 C. The excess liquid was sucked out, and thediisopropanolamine trinitrate was spread out to dry. The dried productwas a white chalky material. 167.6 grams were obtained amounting to77.5% of the theoretical yield.

The dry crude diisopropanolamine trinitrate was then dissolved in 3liters of boiling water, filtered and slowly cooled to 30 C. during thecourse of an hour. The solution was then placed in an ice salt bath andchilled to a temperature of 7 C. The diisopropanolamine trinitrateprecipitated and was then filtered ofi and washed with water to removeacidity. The final purified product obtained was snow white and in theform of uniform, free flowing crystals. The yield obtained amounted to76.6 grams, Since there is some loss due to the product's dissolving inthe mother liquor and wash water, this yield may be considerablyincreased on subsequent batches of product by successive reuse of themother liquor and wash water.

Example II This example reports tests made to determine the sensitivityof the material.

A 10 kilogram weight was dropped repeatedly from a height of 64 inchesonto the material lying on a steel anvil. No detonations were obtained.

A rod weighing 10%, pounds, and having a hemispherical nose, was letslide down a trough set at various angles so as to impinge upon thematerial placed on an anvil. The angles used and the correspondingvertical height of fall were as follows, the angle being measuredbetween the trough and the horizontal:

Angle: Vertical height 45 inches 45 60 do 55 75 do 65 Using both a steelnose and a brass nose on the rod at each angle and both a brass andsteel anvil with each nose, no detonations were obtained in any case.

These tests indicate that diisopropanolamine trinitrate is lesssensitive than tetryl to impact, and to a combination of impact andfriction.

Example III This example shows the preparation and testing of fuse capscontaining base charges of diisopropanolamine trinitrate. Fuse capshells, 0.222 inch in diameter, were each charged with 0.23 gram ofdiisopropanolamine trinitrate, and this charge was pressed at 150 poundspin pressure. Over the base charge, a primer charge of 0.17 gram ofnitromannite and a flash charge of 0.06 gram of a mixture of 75%diazodinitrophenol and 25% nitromannite were pressed together at 30pounds pin pressure.

These caps were given sand tests in a 200 gram bomb, and an average of55.6 grams of sand was crushed by each cap.

Example IV 25 fuse caps were made similarly to those described inExample III except that they contained 0.29 gram of diisopropanolaminetrinitrate pressed at 150 pounds for a base charge, 0.10 gram ofnitromannite primer charge, and 0.06 gram of diazodinitrophenol andnitromannite flash charge pressed together at 25 pounds. These caps allproduced A plates in the lead plate test.

10 more fuse caps similar to these last but containing only 0.08 gram ofnitromannite primer charge were prepared, and these also all produced Alead plates.

Example V 25 electric blasting caps were made up by loading shells 0.260inch in diameter each with 0.29 gram of diisopropanolamine trinitratebase charge and 0.125 gram of nitromannite primer charge pressedtogether under a inch inner capsule at pounds pin pressure and sealingconventional match head assemblies into the tops of the shells. Thesecaps also all produced A lead plates.

The diisopropanolamine trinitrate which was prepared according toExample I and used in all the above tests was a free-flowing crystallinepowder showing admirable charging characteristics.

In its particular use as a base charge in detonators, diisopropanolaminetrinitrate may be used in combination with any primary detonatorcompositions such as, for example, mercury fulminate, lead azide anddiazodinitrophenol. Diisopropanolamine trinitrate is also a usefulmaterial for incorporation with primary detonator compositions. Also,diisopropanolamine trinitrate base charges may be superimposed over orunder other base charge materials such as, for example, tetryl,.pentaerythritol tetranitrate and trinitrotoluene, or it may be employedmixed with such materials.

Its property of relative insolubility in water and its high degree ofstability give diisopropanolamine trinitrate an important advantage overother isopropanolamine nitrates. Monoisopropanolamine dinitrate is verysoluble in water. Triisopropanolamine tetranitrate hydrolyticallydecomposes under all but acid conditions. Furthermore, this salt is onlyobtained in low yields and is too unstable for effective use.

It is readily seen from the above description that diisopropanolaminetrinitrate is a highly useful compound having valuable properties whichdistinguish it from other alkylol amine nitrates. Diisopropanolaminetrinitrate is a practical explosive not only for detonators, but alsofor general explosive uses such as, as an ingredient in blastingexplosives.

What is claimed is:

1. Diisopropanolamine trinitrate.

2. A process of preparing diisopropanolamine trinitrate which comprisesreacting diisopropanolamine with dilute nitric acid, concentrating theresulting solution of nitrate salt of the diisopropanola-mine, reactingthe concentrated product with concentrated nitric acid, drowning thenitration mixture in cold water and separating the precipitateddiisopropanolamine trinitrate product.

3. A process according to claim 2 which further comprises dissolving thediisopropanolamine trinitrate product in hot water, cooling thesolution, and separating the reprecipitated product.

JOHN D. BRANDNER.

